REFRIGERANT-CONTAINING COMPOSITION, USE THEREOF, REFRIGERATOR USING SAME, AND OPERATION METHOD FOR SAID REFRIGERATOR

- DAIKIN INDUSTRIES, LTD.

An object is to provide a novel low-GWP mixed refrigerant. A solution to the problem is to provide a composition containing a refrigerant that contains trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), and 1,3,3,3-tetrafluoropropene (R1234ze).

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Description
TECHNICAL FIELD

The present disclosure relates to a composition containing a refrigerant, use of the composition, a refrigerating machine containing the composition, and a method for operating the refrigerating machine.

BACKGROUND ART

R404A is currently used as a refrigerant for refrigeration apparatuses such as freezing and refrigerating equipment for commercial use. R404A is a three-component mixture refrigerant composed of pentafluoroethane (R125) (44%), 1,1,1-trifluoroethane (R143a) (52%), and 1,1,1,2-tetrafluoroethane (R134a) (4%). However, the global warming potential (GWP) of R404A is 3920. Due to growing concerns over global warming, there is demand for refrigerants with a lower GWP. For this reason, various low-GWP mixed refrigerants that can replace R404A have been proposed (PTL 1 to 5).

CITATION LIST Patent Literature

  • PTL 1: JP2012-526182A
  • PTL 2: JP2013-529703A
  • PTL 3: JP2015-511262A
  • PTL 4: JP2016-156001A
  • PTL 5: W02015/141678A

SUMMARY

A composition comprising a refrigerant, the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), and 1,3,3,3-tetrafluoropropene (R1234ze).

ADVANTAGEOUS EFFECTS

The refrigerant according to the present disclosure has a low GWP.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic view of an apparatus used in a flammability test.

FIG. 2 is a diagram showing points A, C to F, and I to O, and line segments that connect these points in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 99.5 mass %.

FIG. 3 is a diagram showing points A, Br, Er, Fr, Er′, Fr′, Ir, Jr, Ir′, Jr′, Kr, Lr, Mr, Lr′, Mr′, and Nr, and line segments that connect these points in a ternary composition diagram having HFO-1132(E) as a first vertex, R32 as a second vertex, and the mass of 1234ze and R1234yf as a third vertex.

 DESCRIPTION OF EMBODIMENTS

The present inventors conducted intensive research to solve the above problem, and found that a mixed refrigerant containing trans-1,2-difluoroethylene (HFO-1132(E)), 1,3,3,3-tetrafluoropropene (R1234ze), trifluoroethylene (HFO-1123), and difluoromethane (R32) has the above properties.

The present disclosure was completed as a result of further research based on this finding. The present disclosure includes the following embodiments.

Definition of Terms

In the present disclosure, the term “refrigerant” includes at least compounds that are specified in ISO 817 (International Organization for Standardization), and that are given a refrigerant number (ASHRAE number) representing the type of refrigerant with “R” at the beginning; and further includes refrigerants that have properties equivalent to those of such refrigerants, even though a refrigerant number is not yet given. Refrigerants are broadly divided into fluorocarbon compounds and non-fluorocarbon compounds in terms of the structure of the compounds. Fluorocarbon compounds include chlorofluorocarbons (CFC), hydrochlorofluorocarbons (HCFC), and hydrofluorocarbons (HFC). Non-fluorocarbon compounds include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744), and ammonia (R717).

In the present disclosure, the phrase “composition comprising a refrigerant” at least includes (1) a refrigerant itself (including a mixture of refrigerants), (2) a composition that further comprises other components and that can be mixed with at least a refrigeration oil to obtain a working fluid for a refrigerating machine, and (3) a working fluid for a refrigerating machine containing a refrigeration oil. In the present disclosure, of these three embodiments, the composition (2) is referred to as a “refrigerant composition” so as to distinguish it from a refrigerant itself (including a mixture of refrigerants). Further, the working fluid for a refrigerating machine (3) is referred to as a “refrigeration oil-containing working fluid” so as to distinguish it from the “refrigerant composition.”

In the present disclosure, when the term “alternative” is used in a context in which the first refrigerant is replaced with the second refrigerant, the first type of “alternative” means that equipment designed for operation using the first refrigerant can be operated using the second refrigerant under optimum conditions, optionally with changes of only a few parts (at least one of the following: refrigeration oil, gasket, packing, expansion valve, dryer, and other parts) and equipment adjustment. In other words, this type of alternative means that the same equipment is operated with an alternative refrigerant. Embodiments of this type of “alternative” include “drop-in alternative,” “nearly drop-in alternative,” and “retrofit,” in the order in which the extent of changes and adjustment necessary for replacing the first refrigerant with the second refrigerant is smaller.

The term “alternative” also includes a second type of “alternative,” which means that equipment designed for operation using the second refrigerant is operated for the same use as the existing use achieved with the first refrigerant by using the second refrigerant. This type of alternative means that the same use is achieved with an alternative refrigerant.

In the present disclosure, the term “refrigerating machine” (refrigerator) refers to machines in general that draw heat from an object or space to make its temperature lower than the temperature of ambient air, and maintain a low temperature. In other words, refrigerating machines refer to conversion machines that gain energy from the outside to do work, and that perform energy conversion, in order to transfer heat from where the temperature is lower to where the temperature is higher.

In the present disclosure, “a refrigerant having WCF lower-flammability” means that a most flammable formulation (worst case of formulation for flammability) in accordance with U.S. ANSI/ASHRAE Standard 34-2013 has a burning velocity of 10 cm/s or less. In the present disclosure, “a refrigerant having an ASHRAE lower-flammability” means that the WCF burning velocity is 10 cm/s or less, and that the most flammable faction formulation (worst case of fractionation for flammability: WCFF) determined by conducting a leakage test in storage, shipping, and use in accordance with ANSI/ASHRAE Standard 34-2013 by using WCF has a burning velocity of 10 cm/s or less, and is classified under the category of “Class 2L” in the flammability classification of U.S. ANSI/ASHRAE Standard 34-2013.

1. Refrigerant 1.1 Refrigerant Component

The refrigerant according to the present disclosure contains trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), and 1,3,3,3-tetrafluoropropene (R1234ze).

The refrigerant according to the present disclosure may contain, as R1234ze, either R1234ze(E) or R1234ze(Z), or both, and preferably contains only R1234ze(E).

The refrigerant according to the present disclosure has a low GWP.

The refrigerant is preferably as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments IJ, JK, KF, FE, and EI, which connect the following 5 points, or fall on any of line segments IJ, JK, KF, and FE:

point I (70.3, 1.0, 28.7),
point J (57.1, 10.0, 32.9),
point K (45.4, 21.8, 32.8),
point F (2.8, 21.6, 75.6), and
point E (30.2, 1.0, 68.8),

line segments KF and EI are straight lines,

coordinates (x,y,z) of a point on line segment IJ are represented by (x, 0.00991x2−1.945x+88.734, −0.00991x2+0.945x+11.266),

coordinates (x,y,z) of a point on line segment JK are represented by (x, 0.01605x2−2.6528x+109.17, −0.01605x2+1.6528x−9.17), and

coordinates (x,y,z) of a point on line segment FE are represented by (x, 0.0017x2−0.8094x+23.852, −0.0017x2−0.1906x+76.148).

In this case, the refrigerant according to the present disclosure has a refrigerating capacity of 70% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of WCF lower flammability.

The refrigerant is preferably as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments IJ, JK, KD, DC, and CI, which connect the following 5 points, or fall on any of the line segments:

point I (70.3, 1.0, 28.7),
point J (57.1, 10.0, 32.9),
point K (45.4, 21.8, 32.8),
point D (10.7, 21.6, 67.7), and
point C (38.6, 1.0, 60.4),

line segments KD and CI are straight lines,

coordinates (x,y,z) of a point on line segment IJ are represented by (x, 0.00991x2−1.945x+88.734, −0.00991x2+0.945x+11.266),

coordinates (x,y,z) of a point on line segment JK are represented by (x, 0.01605x2−2.6528x+109.17, −0.01605x2+1.6528x−9.17), and

coordinates (x,y,z) of a point on line segment DC are represented by (x, 0.00195x2−0.8346x+30.307, −0.00195x2−0.1654x+69.693).

In this case, the refrigerant according to the present disclosure has a refrigerating capacity of 80% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of WCF lower flammability.

The refrigerant is preferably as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments LM, MN, NF, FE, and EL, which connect the following 5 points, or fall on any of the line segments:

point L (34.8, 1.0, 64.2),
point M (20.4, 10.0, 69.6),
point N (17.1, 21.6, 61.3),
point F (2.8, 21.6, 75.6), and
point E (30.2, 1.0, 68.8),

line segments NF and EL are straight lines,

coordinates (x,y,z) of a point on line segment LM are represented by (x, 0.0399x2−2.8271x+51.071, −0.0399x2+1.8271x+48.929),

coordinates (x,y,z) of a point on line segment MN are represented by (x, 0.9452x2−38.959x+411.42, −0.9452x2+37.959x−311.42), and

coordinates (x,y,z) of a point on line segment FE are represented by (x, 0.0017x2−0.8094x+23.852, −0.0017x2−0.1906x+76.148).

In this case, the refrigerant according to the present disclosure has a refrigerating capacity of 70% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of ASHRAE lower flammability.

The refrigerant is preferably as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments ON, ND, and DO, which connect the following 3 points, or fall on any of line segments ON, ND, and DO:

point O (18.1, 15.8, 66.1),
point N (17.1, 21.6, 61.3), and
point D (10.7, 21.6, 67.7),

line segment ND is a straight line,

coordinates (x,y,z) of a point on line segment ON are represented by (x, 0.9452x2−38.959x+411.42, −0.9452x2+37.959x−311.42), and

coordinates (x,y,z) of a point on line segment DO are represented by (x, 0.00195x2−0.8346x+30.307, −0.00195x2−0.1654x+69.693).

In this case, the refrigerant according to the present disclosure has a refrigerating capacity of 80% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of ASHRAE lower flammability.

The refrigerant according to the present disclosure may further contain 2,3,3,3-tetrafluoropropene (R1234yf).

The refrigerant is preferably as follows: when the mass % of HFO-1132(E) is x, the mass % of R32 is y, and the total mass % of R1234ze and R1234yf is z based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and r=R1234yf/(R1234ze+R1234yf) in the refrigerant,

in a ternary composition diagram having HFO-1132(E) as a first vertex, R32 as a second vertex, and the sum of 1234ze and R1234yf as a third vertex,

when 0.1030≥r>0, coordinates (x,y,z) fall within a figure surrounded by straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrFr, FrE′r, E′rEr, and ErIr, which connect the following 8 points, or fall on any of the straight lines:

point Ir (70.3, 1.0, 28.7),
point I′r (63.8, 5.0, 31.2),
point Jr (57.1, 10.0, 32.9),
point J′r (51.6, 15.0, 33.4),
point Kr (45.4, 21.8, 32.8),
point Fr (−17.476r+2.8, 21.6, 17.476r+75.6),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78),

when 1.0>r>0.103, coordinates (x,y,z) fall within a figure surrounded by straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrBr, BrFr, FrE′r, E′rEr, and ErIr, which connect the following 9 points, or fall on any of the straight lines:

point Ir (70.3, 1.0, 28.7),
point I′r (63.8, 5.0, 31.2),
point Jr (57.1, 10.0, 32.9),
point J′r (51.6, 15.0, 33.4),
point Kr (45.4, 21.8, 32.8),
point Br (1.0, 0.1885r2+0.0694+21.543, −0.1885r2−0.0694+77.457)
point Fr (1.0, 1.6787r2−15.118r+23.139, −1.6787r2+15.118r+75.861),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78).

In this case, the refrigerant according to the present disclosure has a refrigerating capacity of 70% or more relative to R404A, and is classified under the category of WCF lower flammability.

The refrigerant is preferably as follows: when the mass % of HFO-1132(E) is x, the mass % of R32 is y, and the total mass % of R1234ze and R1234yf is z based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and r=R1234yf/(R1234ze+R1234yf) in the refrigerant,

in a ternary composition diagram having HFO-1132(E) as a first vertex, R32 as a second vertex, and the sum of 1234ze and R1234yf as a third vertex,

when 0.1030≥r>0, coordinates (x,y,z) fall within a figure surrounded by straight lines LrI′r, L′rMr, MrM′r, M′rNr, NrFr, FrE′r, E′rEr, and ErIr, which connect the following 8 points, or fall on any of the straight lines:

point Lr (−5.5999r2+20.0r+34.87, 1.0, 5.5999r2−20.0r+64.2),
point L′r (−4.5644r2+18.673r+25.41, 5.0, 4.5644r2−18.673r+69.59),
point Mr (−3.8003r2+15.899r+20.401, 10.0, 3.8003r2−15.899r+69.599),
point M′r (−3.0027r2+13.693r+18.309, 15.0, 3.0027r2−13.693r+66.691),
point Nr (−1.7082r2+11.022r+17.134, 0.3345r+21.594, 1.7082r2−11.3565r+61.272),
point Fr (−17.476r+2.8, 21.6, 17.476r+75.6),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78),

when 1.0>r>0.103, coordinates (x,y,z) fall within a figure surrounded by straight lines LrL′r, L′rMr, MrM′r, M′rNr, NrBr, BrFr, FrE′r, E′rEr, and ErIr, which connect the following 9 points, or fall on any of the straight lines:

point Lr (−5.5999r2+20.0r+34.87, 1.0, 5.5999r2−20.0r+64.2),
point L′r (−4.5644r2+18.673r+25.41, 5.0, 4.5644r2−18.673r+69.59),
point Mr (−3.8003r2+15.899r+20.401, 10.0, 3.8003r2−15.899r+69.599),
point M′r (−3.0027r2+13.693r+18.309, 15.0, 3.0027r2−13.693r+66.691),
point Nr (−1.7082r2+11.022r+17.134, 0.3345r+21.594, 1.7082r2−11.3565r+61.272),
point Br (1.0, 0.1885r2+0.0694r+21.543, −0.1885r2−0.0694r+77.457)
point Fr (1.0, 1.6787r2−15.118r+23.139, −1.6787r2+15.118r+75.861),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78).

In this case, the refrigerant according to the present disclosure has a refrigerating capacity of 70% or more relative to R404A, and is classified under the category of ASHRAE lower flammability.

The refrigerant according to the present disclosure may further contain other additional refrigerants in addition to HFO-1132(E), R32, R1234ze, and R1234yf, as long as the above properties and effects are not impaired. In this respect, the refrigerant according to the present disclosure contains HFO-1132(E), R32, and R1234ze in a total amount of preferably 99.5 mass % or more, more preferably 99.75 mass % or more, and still more preferably 99.9 mass % or more based on the entire refrigerant. In another embodiment, the refrigerant according to the present disclosure contains HFO-1132(E), R32, R1234ze, and R1234yf in a total amount of preferably 99.5 mass % or more, more preferably 99.75 mass % or more, and still more preferably 99.9 mass % or more, based on the entire refrigerant.

Such additional refrigerants are not limited, and can be selected from a wide range of refrigerants. The mixed refrigerant may contain a single additional refrigerant, or two or more additional refrigerants.

1.2 Use

The refrigerant according to the present disclosure can be preferably used as a working fluid in a refrigerating machine.

The composition according to the present disclosure is suitable for use as an alternative refrigerant for R404A.

2. Refrigerant Composition

The refrigerant composition according to the present disclosure contains at least the refrigerant according to the present disclosure, and can be used for the same use as the refrigerant according to the present disclosure. Moreover, the refrigerant composition according to the present disclosure can be further mixed with at least a refrigeration oil to thereby obtain a working fluid for a refrigerating machine.

The refrigerant composition according to the present disclosure further contains at least one other component in addition to the refrigerant according to the present disclosure. The refrigerant composition according to the present disclosure may contain at least one of the following other components, if necessary. As described above, when the refrigerant composition according to the present disclosure is used as a working fluid in a refrigerating machine, it is generally used as a mixture with at least a refrigeration oil. Therefore, it is preferable that the refrigerant composition according to the present disclosure does not substantially contain a refrigeration oil. Specifically, in the refrigerant composition according to the present disclosure, the content of the refrigeration oil based on the entire refrigerant composition is preferably 0 to 1 mass, and more preferably 0 to 0.1 mass %.

2.1. Water

The refrigerant composition according to the present disclosure may contain a small amount of water. The water content of the refrigerant composition is preferably 0.1 mass % or less based on the entire refrigerant. A small amount of water contained in the refrigerant composition stabilizes double bonds in the molecules of unsaturated fluorocarbon compounds that can be present in the refrigerant, and makes it less likely that the unsaturated fluorocarbon compounds will be oxidized, thus increasing the stability of the refrigerant composition.

2.2. Tracer

A tracer is added to the refrigerant composition according to the present disclosure at a detectable concentration such that when the refrigerant composition has been diluted, contaminated, or undergone other changes, the tracer can trace the changes.

The refrigerant composition according to the present disclosure may contain a single tracer, or two or more tracers.

The tracer is not limited, and can be suitably selected from commonly used tracers.

Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrous oxide (NH2O). The tracer is particularly preferably a hydrofluorocarbon, hydrochlorofluorocarbon, chlorofluorocarbon, hydrochlorocarbon, fluorocarbon, or fluoroether.

The following compounds are preferable as the tracer.

FC-14 (tetrafluoromethane, CF4)
HCC-40 (chloromethane, CH3Cl)
HFC-23 (trifluoromethane, CHF3)
HFC-41 (fluoromethane, CH3Cl)
HFC-125 (pentafluoroethane, CF3CHF2)
HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F)
HFC-134 (1,1,2,2-tetrafluoroethane, CHF2CHF2)
HFC-143a (1,1,1-trifluoroethane, CF3CH3)
HFC-143 (1,1, 2-trifluoroethane, CHF2CH2F)
HFC-152a (1, 1-difluoroethane, CHF2CH3)
HFC-152 (1,2-difluoroethane, CH2FCH2F)
HFC-161 (fluoroethane, CH3CH2F)
HFC-245fa (1,1,1,3,3-pentafluoropropane, CF3CH2CHF2)
HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF3CH2CF3)
HFC-236ea (1,1,1,2,3,3-hexafluoropropane, CF3CHFCHF2)
HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane, CF3CHFCF3)
HCFC-22 (chlorodifluoromethane, CHClF2)
HCFC-31 (chlorofluoromethane, CH2ClF)
CFC-1113 (chlorotrifluoroethylene, CF2═CClF)
HFE-125 (trifluoromethyl-difluoromethyl ether, CF3OCHF2)
HFE-134a (trifluoromethyl-fluoromethyl ether, CF3OCH2F)
HFE-143a (trifluoromethyl-methyl ether, CF3OCH3)
HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF3OCHFCF3)
HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3)

The refrigerant composition according to the present disclosure may contain a tracer in a total amount of about 10 parts per million by weight (ppm) to about 1000 ppm based on the entire refrigerant composition. The refrigerant composition according to the present disclosure may contain a tracer in a total amount of preferably about 30 ppm to about 500 ppm, and more preferably about 50 ppm to about 300 ppm, based on the entire refrigerant composition.

2.3. Ultraviolet Fluorescent Dye

The refrigerant composition according to the present disclosure may contain a single ultraviolet fluorescent dye, or two or more ultraviolet fluorescent dyes.

The ultraviolet fluorescent dye is not limited, and can be suitably selected from commonly used ultraviolet fluorescent dyes.

Examples of ultraviolet fluorescent dyes include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, fluorescein, and derivatives thereof. The ultraviolet fluorescent dye is particularly preferably either naphthalimide or coumarin, or both.

2.4. Stabilizer

The refrigerant composition according to the present disclosure may contain a single stabilizer, or two or more stabilizers.

The stabilizer is not limited, and can be suitably selected from commonly used stabilizers.

Examples of stabilizers include nitro compounds, ethers, and amines.

Examples of nitro compounds include aliphatic nitro compounds, such as nitromethane and nitroethane; and aromatic nitro compounds, such as nitrobenzene and nitrostyrene.

Examples of ethers include 1,4-dioxane.

Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

Examples of stabilizers also include butylhydroxyxylene and benzotriazole.

The content of the stabilizer is not limited. Generally, the content of the stabilizer is preferably 0.01 to 5 mass %, and more preferably 0.05 to 2 mass %, based on the entire refrigerant.

2.5. Polymerization Inhibitor

The refrigerant composition according to the present disclosure may contain a single polymerization inhibitor, or two or more polymerization inhibitors.

The polymerization inhibitor is not limited, and can be suitably selected from commonly used polymerization inhibitors.

Examples of polymerization inhibitors include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

The content of the polymerization inhibitor is not limited. Generally, the content of the polymerization inhibitor is preferably 0.01 to 5 mass %, and more preferably 0.05 to 2 mass %, based on the entire refrigerant.

3. Refrigeration Oil-Containing Working Fluid

The refrigeration oil-containing working fluid according to the present disclosure contains at least the refrigerant or refrigerant composition according to the present disclosure and a refrigeration oil, and is used as a working fluid in a refrigerating machine. Specifically, the refrigeration oil-containing working fluid according to the present disclosure is obtained by mixing a refrigeration oil used in a compressor of a refrigerating machine with the refrigerant or the refrigerant composition. The refrigeration oil-containing working fluid generally contains 10 to 50 mass % of refrigeration oil.

3.1. Refrigeration Oil

The composition according to the present disclosure may contain a single refrigeration oil, or two or more refrigeration oils.

The refrigeration oil is not limited, and can be suitably selected from commonly used refrigeration oils. In this case, refrigeration oils that are superior in the action of increasing the miscibility with the mixture and the stability of the mixture, for example, are suitably selected as necessary.

The base oil of the refrigeration oil is preferably, for example, at least one member selected from the group consisting of polyalkylene glycols (PAG), polyol esters (POE), and polyvinyl ethers (PVE).

The refrigeration oil may further contain additives in addition to the base oil. The additive may be at least one member selected from the group consisting of antioxidants, extreme-pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust inhibitors, oil agents, and antifoaming agents.

A refrigeration oil with a kinematic viscosity of 5 to 400 cSt at 40° C. is preferable from the standpoint of lubrication.

The refrigeration oil-containing working fluid according to the present disclosure may further optionally contain at least one additive. Examples of additives include the compatibilizing agents described below.

3.2. Compatibilizing Agent

The refrigeration oil-containing working fluid according to the present disclosure may contain a single compatibilizing agent, or two or more compatibilizing agents.

The compatibilizing agent is not limited, and can be suitably selected from commonly used compatibilizing agents.

Examples of compatibilizing agents include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes. The compatibilizing agent is particularly preferably a polyoxyalkylene glycol ether.

4. Method for Operating Refrigerating Machine

The method for operating a refrigerating machine according to the present disclosure is a method for operating a refrigerating machine using the refrigerant according to the present disclosure.

Specifically, the method for operating a refrigerating machine according to the present disclosure includes circulating the refrigerant according to the present disclosure in a refrigerating machine.

The embodiments are described above; however, it will be understood that various changes in forms and details can be made without departing from the spirit and scope of the claims.

Item 1.

A composition comprising a refrigerant, the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), and 1,3,3,3-tetrafluoropropene (R1234ze).

Item 2.

The composition according to Item 1,

wherein

when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments IJ, JK, KF, FE, and EI, which connect the following 5 points, or fall on any of the line segments:

point I (70.3, 1.0, 28.7),
point J (57.1, 10.0, 32.9),
point K (45.4, 21.8, 32.8),
point F (2.8, 21.6, 75.6), and
point E (30.2, 1.0, 68.8),

line segments KF and EI are straight lines,

coordinates (x,y,z) of a point on line segment IJ are represented by (x, 0.00991x2−1.945x+88.734, −0.00991x2+0.945x+11.266),

coordinates (x,y,z) of a point on line segment JK are represented by (x, 0.01605x2−2.6528x+109.17, −0.01605x2+1.6528x−9.17), and

coordinates (x,y,z) of a point on line segment FE are represented by (x, 0.0017x2−0.8094x+23.852, −0.0017x2−0.1906x+76.148).

Item 3.

The composition according to Item 1,

wherein

when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments IJ, JK, KD, DC, and CI, which connect the following 5 points, or fall on any of line segments IJ, JK, KD, and DC:

point I (70.3, 1.0, 28.7),
point J (57.1, 10.0, 32.9),
point K (45.4, 21.8, 32.8),
point D (10.7, 21.6, 67.7), and
point C (38.6, 1.0, 60.4),

line segments KD and CI are straight lines,

coordinates (x,y,z) of a point on line segment IJ are represented by (x, 0.00991x2−1.945x+88.734, −0.00991x2+0.945x+11.266),

coordinates (x,y,z) of a point on line segment JK are represented by (x, 0.01605x2−2.6528x+109.17, −0.01605x2+1.6528x−9.17), and

coordinates (x,y,z) of a point on line segment DC are represented by (x, 0.00195x2−0.8346x+30.307, −0.00195x2−0.1654x+69.693).

Item 4.

The composition according to Item 1,

wherein

when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments LM, MN, NF, FE, and EL, which connect the following 5 points, or fall on any of line segments LM, MN, NF, and FE:

point L (34.8, 1.0, 64.2),
point M (20.4, 10.0, 69.6),
point N (17.1, 21.6, 61.3),
point F (2.8, 21.6, 75.6), and
point E (30.2, 1.0, 68.8),

line segments NF and EL are straight lines,

coordinates (x,y,z) of a point on line segment LM are represented by (x, 0.0399x2−2.8271x+51.071, −0.0399x2+1.8271x+48.929),

coordinates (x,y,z) of a point on line segment MN are represented by (x, 0.9452x2−38.959x+411.42, −0.9452x2+37.959x−311.42), and

coordinates (x,y,z) of a point on line segment FE are represented by (x, 0.0017x2−0.8094x+23.852, −0.0017x2−0.1906x+76.148).

Item 5.

The composition according to Item 1,

wherein

when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments ON, ND, and DO, which connect the following 3 points, or fall on any of line segments ON, ND, and DO:

point O (18.1, 15.8, 66.1),
point N (17.1, 21.6, 61.3), and
point D (10.7, 21.6, 67.7),

line segment ND is a straight line,

coordinates (x,y,z) of a point on line segment ON are represented by (x, 0.9452x2−38.959x+411.42, −0.9452x2+37.959x−311.42), and

coordinates (x,y,z) of a point on line segment DO are represented by (x, 0.00195x2−0.8346x+30.307, −0.00195x2−0.1654x+69.693).

Item 6.

The composition according to any one of Items 1 to 5, wherein the refrigerant further comprises 2,3,3,3-tetrafluoropropene (R1234yf).

Item 7.

The composition according to Item 6,

wherein

when the mass % of HFO-1132(E) is x, the mass % of R32 is y, and the total mass % of R1234ze and R1234yf is z based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and r=R1234yf/(R1234ze+R1234yf) in the refrigerant,

in a ternary composition diagram having HFO-1132(E) as a first vertex, R32 as a second vertex, and the sum of 1234ze and R1234yf as a third vertex,

when 0.103≥r>0, coordinates (x,y,z) fall within a figure surrounded by straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrFr, FrE′r, E′rEr, and ErIr, which connect the following 8 points, or fall on any of straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrFr, FrE′r, and E′rEr:

point Ir (70.3, 1.0, 28.7),
point I′r (63.8, 5.0, 31.2),
point Jr (57.1, 10.0, 32.9),
point J′r (51.6, 15.0, 33.4),
point Kr (45.4, 21.8, 32.8),
point Fr (−17.476r+2.8, 21.6, 17.476r+75.6),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78),

when 1.0>r>0.103, coordinates (x,y,z) fall within a figure surrounded by straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrBr, BrE′r, FrE′r, E′rEr, and ErIr, which connect the following 9 points, or fall on any of straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrBr, BrFr, FrEr′, and Er′Er:

point Ir (70.3, 1.0, 28.7),
point I′r (63.8, 5.0, 31.2),
point Jr (57.1, 10.0, 32.9),
point J′r (51.6, 15.0, 33.4),
point Kr (45.4, 21.8, 32.8),
point Br (1.0, 0.1885r2+0.0694+21.543, −0.1885r2−0.0694r+77.457)
point Fr (1.0, 1.6787r2−15.118r+23.139, −1.6787r2+15.118r+75.861),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78).

Item 8.

The composition according to Item 6,

wherein

when the mass % of HFO-1132(E) is x, the mass % of R32 is y, and the total mass % of R1234ze and R1234yf is z based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and r=R1234yf/(R1234ze+R1234yf) in the refrigerant,

in a ternary composition diagram having HFO-1132(E) as a first vertex, R32 as a second vertex, and the sum of 1234ze and R1234yf as a third vertex,

when 0.1030≥r>0, coordinates (x,y,z) fall within a figure surrounded by straight lines LrI′r, L′rMr, MrM′r, M′rNr, NrBr, FrEr, E′rEr, and ErIr, which connect the following 8 points, or fall on any of straight lines LrI′r, L′rMr, MrM′r, M′rNr, NrFr, FrEr, and Erer:

point Lr (−5.5999r2+20.0r+34.8, 1.0, 5.5999r2−20.0r+64.2),
point L′r (−4.5644r2+18.673r+25.41, 5.0, 4.5644r2−18.673r+69.59),
point Mr (−3.8003r2+15.899r+20.401, 10.0, 3.8003r2−15.899r+69.599),
point M′r (−3.0027r2+13.693r+18.309, 15.0, 3.0027r2−13.693r+66.691),
point Nr (−1.7082r2+11.022r+17.134, 0.3345r+21.594, 1.7082r2−11.3565r+61.272),
point Fr (−17.476r+2.8, 21.6, 17.476r+75.6),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78),

when 1.0>r>0.103, coordinates (x,y,z) fall within a figure surrounded by straight lines LrL′r, L′rMr, MrM′r, M′rNr, NrBr, BrFr, FrE′r, E′rEr, and ErIr, which connect the following 9 points, or fall on any of straight lines LrL′r, L′rMr, MrM′r, M′rNr, NrBr, BrFr, FrE′r, and E′rEr:

point Lr (−5.5999r2+20.0r+34.8, 1.0, 5.5999r2−20.0r+64.2),
point L′r (−4.5644r2+18.673r+25.41, 5.0, 4.5644r2−18.673r+69.59),
point Mr (−3.8003r2+15.899r+20.401, 10.0, 3.8003r2−15.899r+69.599),
point M′r (−3.0027r2+13.693r+18.309, 15.0, 3.0027r2−13.693r+66.691),
point Nr (−1.7082r2+11.022r+17.134, 0.3345r+21.594, 1.7082r2−11.3565r+61.272),
point Br (1.0, 0.1885r2+0.0694r+21.543, −0.1885r2−0.0694r+77.457)
point Fr (1.0, 1.6787r2−15.118r+23.139, −1.6787r2+15.118r+75.861),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78).

Item 9.

The composition according to any one of Items 1 to 8, which is for use as a working fluid for a refrigerating machine, the composition further comprising a refrigeration oil.

Item 10.

The composition according to any one of Items 1 to 9, which is for use as an alternative refrigerant for R404A.

Item 11.

Use of the composition of any one of Items 1 to 9 as an alternative refrigerant for R404A.

Item 12.

A refrigerating machine comprising the composition of any one of Items 1 to 9 as a working fluid.

Item 13.

A method for operating a refrigerating machine, comprising circulating the composition of any one of Items 1 to 9 as a working fluid in a refrigerating machine.

EXAMPLES

The present disclosure is described in more detail below with reference to Examples. However, the present disclosure is not limited to the Examples.

Example A

Mixed refrigerants were prepared by mixing HFO-1132(E), R32, and R1234ze in mass % shown in Table 1 based on their sum.

The GWP of R404A (R125=44%/R143A=52%/R134A=4%) and the mixed refrigerants was evaluated based on the values stated in the Intergovernmental Panel on Climate Change (IPCC), fourth assessment report. The GWP of HFO-1132(E), which was not stated therein, was assumed to be 1 from HFO-1132a (GWP=1 or less) and HFO-1123 (GWP=0.3, described in PTL 1). The refrigerating capacity of R404A and the mixed refrigerants was determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) under the following conditions.

The COP and refrigerating capacity of these mixed refrigerants relative to those of R404A were determined. The computational conditions were as follows.

Evaporating temperature: −40° C.
Condensation temperature: 40° C.
Superheating temperature: 20 K
Subcooling temperature: 0 K
Compressor efficiency: 70%

Tables 1 to 3 show these values together with the GWP of each mixed refrigerant. The COP and refrigerating capacity are percentages relative to R410A.

The coefficient of performance (COP) was determined by the following formula.


COP=(refrigerating capacity or heating capacity)/power consumption

TABLE 1 Com Com Exam- Exam- Exam- Com Ex2 Ex3 ple1 Exam- ple3 ple4 Exam- Item Unit Ex1 A B C ple2 D E ple5 HFO-1132 (E) Mass % R404A 76.9 1.0 38.6 25.9 10.7 30.2 17.8 R32 Mass % 22.1 21.5 1.0 10.0 21.6 1.0 10.0 R1234ze Mass % 1.0 77.5 60.4 64.1 67.7 68.8 72.2 GWP — 3922 150 150 11 72 150 11 72 COP Ratio % (Relative 100 105 113 109 110 112 110 111 to R404A) Refrigerating % (Relative 100 170 68 80 80 80 70 70 Capacity Ratio to R404A) Condensation ° C. 0.3 0.4 11.1 9.3 10.8 11.3 10.0 11.4 Glide Exam- Exam- Exam- Exam- Exam- ple6 ple7 Exam- ple9 Exam- ple11 ple12 Exam- Item Unit F I ple8 J ple10 K L ple13 HFO-1132 (E) Mass % 2.8 70.3 63.8 57.1 51.6 45.4 34.8 25.4 R32 Mass % 21.6 1.0 5.0 10.0 15.0 21.8 1.0 5.0 R1234ze Mass % 75.6 28.7 31.2 32.9 33.4 32.8 64.2 69.6 GWP — 150 9 36 70 104 150 11 38 COP Ratio % (Relative 113 106 107 107 107 107 110 110 to R404A) Refrigerating % (Relative 70 119 118 119 121 125 76 71 Capacity Ratio to R404A) Condensation ° C. 11.2 4.3 5.1 5.7 6.0 6.0 9.7 10.7 Glide Exam- Exam- Exam- ple14 Exam- ple16 ple17 Item Unit M ple15 N O HFO-1132 (E) Mass % 20.4 18.3 17.1 18.1 R32 Mass % 10.0 15.0 21.6 15.8 R1234ze Mass % 69.6 66.7 61.3 66.1 GWP — 72 105 150 111 COP Ratio % (Relative 111 111 111 111 to R404A) Refrigerating % (Relative 73 79 88 80 Capacity Ratio to R404A) Condensation ° C. 11.3 11.3 10.8 11.3 Glide

A leak was simulated with the formulation of each mixture as WCF, under the conditions of equipment, storage, shipping, leak, and recharge based on ASHRAE Standard 34-2013, by using the NIST Standard Reference Database Refleak Version 4.0, and the most flammable fraction was determined to be WCFF.

For the flammability, the burning velocity was measured according to ANSI/ASHRAE Standard 34-2013. Compositions having a burning velocity of 10 cm/s or less in both WCF and WCFF were determined to be “Class 2L (lower flammability).”

A burning velocity test was performed using the apparatus shown in FIG. 1 in the following manner. First, the mixed refrigerants were purified to 99.5% or more, and were deaerated by repeating a cycle of freezing, pumping, and thawing until no traces of air were observed on the vacuum gauge. The burning velocity was measured by the closed method. The initial temperature was ambient temperature. Ignition was performed by generating an electric spark between the electrodes in the center of a sample cell. The duration of the discharge was 1.0 to 9.9 ms, and the ignition energy was typically about 0.1 to 1.0 J. The spread of the flame was visualized using schlieren photographs. A cylindrical container (inner diameter: 155 mm, length: 198 mm) equipped with two light-transmissive acrylic windows was used as the sample cell, and a xenon lamp was used as the light source. The propagation of flame was filmed with a schlieren system using a collimating lens and a high-speed digital video camera (frame rate: 600 fps), and recorded as video data on a PC. From the video image, flame propagation rate Sb (cm/sec) was measured. The burning velocity (Su) is expressed by the volume of unburned gas consumed by the flame surface of a unit area per unit time and was calculated by using the following formula.


Su=Sb*ρu/ρb

ρu: adiabatic flame temperature (unburned)
ρb: adiabatic flame temperature (burned)

ρu was calculated from a measurement temperature, and ρb was calculated from the combustion and isobaric specific heat of combustion gas.

Table 2 shows the results.

TABLE 2 Item Unit I I′ J J′ F WCF HFO-1132 (E) Mass % 70.3 63.8 57.1 51.6 45.4 R32 Mass % 1.0 5.0 10.0 15.0 21.8 R1234ze Mass % 28.7 31.2 32.9 33.4 32.8 Burning Velocity (WCF) cm/s 10 10 10 10 10 Item Unit L L′ M M′ N WCF HFO-1132 (E) Mass % 34.8 25.4 20.4 18.3 17.1 R32 Mass % 1.0 5.0 10.0 15.0 21.6 R1234ze Mass % 64.2 69.6 69.6 66.7 61.3 Leak Conditions Forming WCFF Storage Storage Storage Storage Storage and and and and and Shipping - Shipping - Shipping - Shipping - Shipping - 34.5° C., 33.9° C., 34.7° C., 35.9° C., 37.4° C., 0% 0% 0% 0% 0% When When When When When WCFF HFO-1132 (E) Mass % 67.9 54.5 44.2 38.2 33.5 R32 Mass % 2.4 12.3 23.4 32.2 41.0 R1234ze Mass % 29.7 33.2 32.4 29.6 25.5 Burning Velocity (WCF) cm/s 5 or less 5 or less 5 or less 5 or less 5 or less Burning Velocity (WCFF) cm/s 10 10 10 10 10

From these results, it is understood that a mixed refrigerant has a refrigerating capacity of 70% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of WCF lower flammability when the mixed refrigerant is represented as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the mixed refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments IJ, JK, KF, FE, and EI, which connect the following 5 points, or fall on any of the line segments:

point I (70.3, 1.0, 28.7),
point J (57.1, 10.0, 32.9),
point K (45.4, 21.8, 32.8),
point F (2.8, 21.6, 75.6), and
point E (30.2, 1.0, 68.8),

line segments KF and EI are straight lines,

coordinates (x,y,z) of a point on line segment IJ are represented by (x, 0.00991x2−1.945x+88.734, −0.00991x2+0.945x+11.266),

coordinates (x,y,z) of a point on line segment JK are represented by (x, 0.01605x2−2.6528x+109.17, −0.01605x2+1.6528x−9.17), and

coordinates (x,y,z) of a point on line segment FE are represented by (x, 0.0017x2−0.8094x+23.852, −0.0017x2−0.1906x+76.148).

It is also understood that a mixed refrigerant has a refrigerating capacity of 80% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of WCF lower flammability when the mixed refrigerant is represented as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the mixed refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments IJ, JK, KD, DC, and CI, which connect the following 5 points, or fall on any of the line segments:

point I (70.3, 1.0, 28.7),
point J (57.1, 10.0, 32.9),
point K (45.4, 21.8, 32.8),
point D (10.7, 21.6, 67.7), and
point C (38.6, 1.0, 60.4),

line segments KD and CI are straight lines,

coordinates (x,y,z) of a point on line segment IJ are represented by (x, 0.00991x2−1.945x+88.734, −0.00991x2+0.945x+11.266),

coordinates (x,y,z) of a point on line segment JK are represented by (x, 0.01605x2−2.6528x+109.17, −0.01605x2+1.6528x−9.17), and

coordinates (x,y,z) of a point on line segment DC are represented by (x, 0.00195x2−0.8346x+30.307, −0.00195x2−0.1654x+69.693).

It is also understood that a mixed refrigerant has a refrigerating capacity of 70% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of ASHRAE lower flammability when the mixed refrigerant is represented as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the mixed refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments LM, MN, NF, FE, and EL, which connect the following 5 points, or fall on any of the line segments:

point L (34.8, 1.0, 64.2),
point M (20.4, 10.0, 69.6),
point N (17.1, 21.6, 61.3),
point F (2.8, 21.6, 75.6), and
point E (30.2, 1.0, 68.8),

line segments NF and EL are straight lines,

coordinates (x,y,z) of a point on line segment LM are represented by (x, 0.0399x2−2.8271x+51.071, −0.0399x2+1.8271x+48.929),

coordinates (x,y,z) of a point on line segment MN are represented by (x, 0.9452x2−38.959x+411.42, −0.9452x2+37.959x−311.42), and

coordinates (x,y,z) of a point on line segment FE are represented by (x, 0.0017x2−0.8094x+23.852, −0.0017x2−0.1906x+76.148).

It is also understood that a mixed refrigerant has a refrigerating capacity of 80% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of ASHRAE lower flammability when the mixed refrigerant is represented as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the mixed refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments ON, ND, and DO, which connect the following 3 points, or fall on any of line segments ON, ND, and DO:

point O (18.1, 15.8, 66.1),
point N (17.1, 21.6, 61.3), and
point D (10.7, 21.6, 67.7),

line segment ND is a straight line,

coordinates (x,y,z) of a point on line segment ON are represented by (x, 0.9452x2−38.959x+411.42, −0.9452x2+37.959x−311.42), and

coordinates (x,y,z) of a point on line segment DO are represented by (x, 0.00195x2−0.8346x+30.307, −0.00195x2−0.1654x+69.693).

The approximate expressions that represent line segments connecting the points were each determined in the following manner.

TABLE 3 Exam- Exam- Exam- Exam- ple1 Exam- ple3 ple4 Exam- ple6 Item Unit C ple2 D E ple5 F HFO-1132 (E) Mass % 38.6 25.9 10.7 30.2 17.8 2.8 R32 Mass % 1.0 10.0 21.6 1.0 10.0 21.6 R1234ze Mass % 60.4 64.1 67.7 68.8 72.2 75.6 x = HFO-1132 (E) x x Approximate Expression 0.00195x2 − 0.8346x + 30.307 0.0017x2 − 0.8094x + 23.852 of R32 Approximate Expression −0.00195x2 − 0.1654x + 69.693 −0.0017x2 − 0.1906x + 76.148 of R1234ze Exam- Exam- Exam- Exam- ple7 Exam- ple9 ple9 Exam- ple11 Item Unit I ple8 J J ple10 K HFO-1132 (E) Mass % 70.3 63.8 57.1 57.1 51.6 45.4 R32 Mass % 1.0 5.0 10.0 10.0 15.0 21.8 R1234ze Mass % 28.7 31.2 32.9 32.9 33.4 32.8 x = HFO-1132 (E) x x Approximate Expression 0.00991x2 − 1.945x + 88.734 0.01605x2 − 2.6528x + 109.17 of R32 Approximate Expression −0.00991x2 + 0.945x + 11.266 −0.01605x2 + 1.6528x − 9.17 of R1234ze Exam- Exam- Exam- Exam- ple12 Exam- ple14 ple14 Exam- ple16 Item Unit L ple13 M M ple15 N HFO-1132 (E) Mass % 34.8 25.4 20.4 20.4 18.3 17.1 R32 Mass % 1.0 5.0 10.0 10.0 15.0 21.6 R1234ze Mass % 64.2 69.6 69.6 69.6 66.7 61.3 x = HFO-1132 (E) x x Approximate Expression 0.0399x2 − 2.8271x + 51.071 0.9452x2 − 38.959x + 411.42 of R32 Approximate Expression −0.0399x2 + 1.8271x + 48.929 −0.9452x2 + 37.959x − 311.42 of R1234ze

Example B

Mixed refrigerants were prepared such that the mass % of HFO-1132(E), the mass % of R32, and the total mass % of R1234ze and R1234yf were as shown in Tables 4 and 5 based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and evaluated in the same manner as in Example A. Tables 4 and 5 show the results. The alphabetical letter “r” represents R1234yf/(R1234ze+R1234yf).

TABLE 4 Com Com Exam- Exam- Exam- Exam- Exam- Exam- Ex4 Ex5 ple18 ple19 ple20 ple21 ple22 ple23 Item Unit Ar = 0.103 Br = 0.103 Er = 0.103 E′r = 0.103 Fr = 0.103 Ir = 0.103 I′r = 0.103 Jr = 0.103 HFO-1132 (E) Mass % 76.9 1.0 28.5 16.0 1.0 70.3 63.8 57.1 R32 Mass % 22.1 21.6 1.0 10.0 21.6 1.0 5.0 10.0 R1234(ze + yf) Mass % 1.0 77.4 70.5 74.0 77.4 28.7 31.2 32.9 GWP — 150 150 11 72 150 9 36 70 COP Ratio % (Relative 105 112 110 111 112 106 106 107 to R404A) Refrigerating % (Relative 170 70 70 70 70 120 119 120 Capacity Ratio to R404A) Condensation ° C. 0.4 10.7 9.6 10.9 10.7 4.1 4.8 5.4 Glide Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple24 ple25 ple26 ple27 ple28 ple29 ple30 Item Unit J′r = 0.103 Kr = 0.103 Lr = 0.103 L′r = 0.103 Mr = 0.103 M′r = 0.103 Nr = 0.103 HFO-1132 (E) Mass % 51.6 45.4 36.8 27.3 22.0 19.7 18.3 R32 Mass % 15.0 21.8 1.0 5.0 10.0 15.0 21.6 R1234(ze + yf) Mass % 33.4 32.8 62.2 67.7 68.0 65.3 60.1 GWP — 104 150 11 38 72 105 149 COP Ratio % (Relative 107 107 109 110 110 110 111 to R404A) Refrigerating % (Relative 122 127 80 75 77 83 92 Capacity Ratio to R404A) Condensation ° C. 5.7 5.7 9.0 10.1 10.7 10.7 10.1 Glide Com Com Exam- Exam- Exam- Exam- Exam- Exam- Ex6 Ex7 ple31 ple32 ple33 ple34 ple35 ple36 Item Unit Ar = 0.5 Br = 0.5 Er = 0.5 E′r = 0.5 Fr = 0.5 Ir = 0.5 I′r = 0.5 Jr = 0.5 HFO-1132 (E) Mass % 76.9 1.0 21.8 9.2 1.0 70.3 63.8 57.1 R32 Mass % 22.1 21.6 1.0 10.0 16.0 1.0 5.0 10.0 R1234(ze + yf) Mass % 1.0 77.4 77.2 80.8 83.0 28.7 31.2 32.9 GWP — 150 150 11 72 112 9 36 70 COP Ratio % (Relative 105 110 108 109 110 106 106 106 to R404A) Refrigerating % (Relative 170 79 70 70 70 125 125 126 Capacity Ratio to R404A) Condensation ° C. 0.3 8.9 7.9 9.1 8.9 3.1 3.7 4.2 Glide

TABLE 5 Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple37 ple38 ple39 ple40 ple41 ple42 ple43 Item Unit J′r = 0.5 Kr = 0.5 Lr = 0.5 L′r = 0.5 Mr = 0.5 M′r = 0.5 Nr = 0.5 HFO-1132 (E) Mass % 51.6 45.4 43.4 33.6 27.4 24.4 22.2 R32 Mass % 15.0 21.8 1.0 5.0 10.0 15.0 21.8 R1234(ze + yf) Mass % 33.4 32.8 55.6 61.4 62.6 60.6 56.0 GWP — 103 149 10 37 71 105 150 COP Ratio % (Relative 106 106 107 107 108 108 108 to R404A) Refrigerating % (Relative 129 133 95 90 92 97 105 Capacity Ratio to R404A) Condensation ° C. 4.4 4.3 6.4 7.6 8.2 8.2 7.6 Glide Com Com Com Com Com Com Com Com Ex8 Ex9 Ex10 Ex11 Ex12 Ex13 Ex14 Ex15 Item Unit Ar = 1 Br = 1 Cr = 1 C′r = 1 Ir = 1 I′r = 1 Jr = 1 J′r = 1 HFO-1132 (E) Mass % 76.9 1.0 13.6 1.0 70.3 63.8 57.1 51.6 R32 Mass % 22.1 21.8 1.0 9.7 1.0 5.0 10.0 15.0 R1234(ze + yf) Mass % 1.0 77.2 85.4 89.3 28.7 31.2 32.9 33.4 GWP — 150 150 10 69 9 36 69 103 COP Ratio % (Relative 105 108 106 107 105 105 105 105 to R404A) Refrigerating % (Relative 170 90 70 70 132 132 134 137 Capacity Ratio to R404A) Condensation ° C. 0.3 6.8 5.8 6.7 1.9 2.4 2.7 2.9 Glide Com Com Com Com Com Com Ex16 Ex17 Ex18 Ex19 Ex20 Ex21 Item Unit Kr = 1 Lr = 1 L′r = 1 Mr = 1 M′r = 1 Nr = 1 HFO-1132 (E) Mass % 45.4 49.2 39.2 32.5 29.0 26.2 R32 Mass % 21.8 1.0 5.0 10.0 15.0 21.9 R1234(ze + yf) Mass % 32.8 49.8 55.8 57.5 56.0 51.9 GWP — 149 9 36 70 104 150 COP Ratio % (Relative 105 105 105 106 106 106 to R404A) Refrigerating % (Relative 141 110 106 108 112 120 Capacity Ratio to R404A) Condensation ° C. 2.8 3.9 5.0 5.5 5.4 4.8 Glide

The coordinates of each point were determined by using an approximate expression in the following manner.

TABLE 6 A Point Ar (r = R1234yf/ Point Br (r = R1234yf/ (R1234(ze + yf) (R1234(ze + yf) Item Unit 0.0 0.103 0.5 1.0 0.0 0.103 0.5 1 HFO-1132 (E) Mass % 76.9 76.9 76.9 76.9 1.0 1.0 1.0 1.0 R32 Mass % 22.1 22.1 22.1 22.1 21.5 21.6 21.6 21.8 R1234(ze + yf) Mass % 1.0 1.0 1.0 1.0 77.5 77.4 77.4 77.2 x = HFO-1132 (E) 76.9 1.0 y = R32 22.1 0.1885r2 + 0.0694r + 21.543 z = R1234(ze + yf) 1.0 −0.1885r2 − 0.0694r + 77.457 Point Er (r = R1234yf/ Point E′r (Midpoint (R1234(ze + yf) between Er and Fr) Item Unit 0.0 0.103 0.5 1.0 0.0 0.103 0.5 0.967 HFO-1132 (E) Mass % 30.2 28.5 21.8 13.6 17.8 16.0 9.2 1.0 R32 Mass % 1.0 1.0 1.0 1.0 10.0 10.0 10.0 10.0 R1234(ze + yf) Mass % 68.8 70.5 77.2 85.4 72.2 74.0 80.8 89.0 x = HFO-1132 (E) 0.3938r2 − 17.016r + 30.22 −0.3615r2 − 17.002r + 17.781 y = R32 1.0 10.0 z = R1234(ze + yf) −0.3938r2 + 17.016r + 68.78 0.3615r2 + 17.002r + 72.219 Point Fr (r = R1234yf/ (R1234(ze + yf)) Item Unit 0 0.103 0.103 0.5 1 HFO-1132 (E) Mass % 2.8 1.0 1.0 1.0 1.0 R32 Mass % 21.6 21.6 21.6 16.0 9.7 R1234(ze + yf) Mass % 75.6 77.4 77.4 83.0 89.3 x = HFO-1132 (E) −17.476r + 2.8 1.0 y = R32 21.6 1.6787r2 − 15.118r + 23.139 z = R1234(ze + yf) 17.476r + 75.6 −1.6787r2 + 15.118r + 75.861 Point Ir (r = R1234yf/ Point I′r (Midpoint Point Jr (r = R1234yf/ (R1234(ze + yf)) between Ir and Jr) (R1234(ze + yf)) Item Unit 0.0 0.103 0.5 1.0 0.0 0.103 0.5 0.967 0.0 0.103 0.5 1.0 HFO-1132 (E) Mass % 70.3 70.3 70.3 70.3 63.8 63.8 63.8 63.8 57.1 57.1 57.1 57.1 R32 Mass % 1.0 1.0 1.0 1.0 5.0 5.0 5.0 5.0 10.0 10.0 10.0 10.0 R1234(ze + yf) Mass % 28.7 28.7 28.7 28.7 31.2 31.2 31.2 31.2 32.9 32.9 32.9 32.9 x = HFO-1132 (E) 70.3 63.8 57.1 y = R32 1.0 5.0 10.0 z = R1234(ze + yf) 28.7 31.2 32.9

TABLE 7 Point J′r (Midpoint Point Kr (r = R1234yf/ between Jr and Kr) (R1234(ze + yf)) Item Unit 0.0 0.103 0.5 0.967 0.0 0.103 0.5 0.967 HFO-1132 (E) Mass % 51.6 51.6 51.6 51.6 45.4 45.4 45.4 45.4 R32 Mass % 15.0 15.0 15.0 15.0 21.8 21.8 21.8 21.8 R1234(ze + yf) Mass % 33.4 33.4 33.4 33.4 32.8 32.8 32.8 32.8 x = HFO-1132 (E) 51.6 45.4 y = R32 15.0 21.8 z = R1234(ze + yf) 33.4 32.8 Point Lr (r = R1234yf/ Point L′r (Midpoint Point Mr (r = R1234yf/ (R1234(ze + yf)) between Lr and Mr) (R1234(ze + yf)) Item Unit 0.0 0.103 0.5 1.0 0.0 0.103 0.5 0.967 0.0 0.103 0.5 1.0 HFO-1132 (E) Mass % 34.8 36.8 43.4 49.2 25.4 27.3 33.6 39.2 20.4 22.0 27.4 32.5 R32 Mass % 1.0 1.0 1.0 1.0 5.0 5.0 5.0 5.0 10.0 10.0 10.0 10.0 R1234(ze + yf) Mass % 64.2 62.2 55.6 49.8 69.6 67.7 61.4 55.8 69.6 68.0 62.6 57.5 x = HFO-1132 (E) −5.5999r2 + 20.0r + 34.8 −4.5544r2 + 18.673r + 25.41 −3.8003r2 + 15.899r + 20.401 y = R32 1.0 5.0 10.0 z = R1234(ze + yf) 5.5999r2 − 20.0r + 64.2 4.5644r2 − 18.673r + 69.59 3.8003r2 − 15.899r + 69.599 Point M′r (Midpoint Point Nr (r = R1234yf/ between Mr and  Nr) (R1234(ze + yf)) Item Unit 0.0 0.103 0.5 1.0 0.0 0.103 0.5 0.967 HFO-1132 (E) Mass % 18.3 19.7 24.4 29.0 17.1 18.3 22.2 26.2 R32 Mass % 15.0 15.0 15.0 15.0 21.6 21.6 21.8 21.9 R1234(ze + yf) Mass % 66.7 65.3 60.6 56.0 61.3 60.1 56.0 51.9 x = HFO-1132 (E) −3.0027r2 + 13.693r + 18.309 −1.7082r2 + 11.022r + 17.134 y = R32 15.0 0.3345r + 21.594 z = R1234(ze + yf) 3.0027r2 − 13.693r + 66.691 1.7082r2 − 11.3565r + 61.272

From these results, it is understood that a mixed refrigerant has a refrigerating capacity of 70% or more relative to R404A and is classified under the category of WCF lower flammability when the mixed refrigerant is represented as follows: when the mass % of HFO-1132(E) is x, the mass % of R32 is y, and the total mass % of R1234ze and R1234yf is z based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and r=R1234yf/(R1234ze+R1234yf) in the mixed refrigerant,

in a ternary composition diagram having HFO-1132(E) as a first vertex, R32 as a second vertex, and the sum of 1234ze and R1234yf as a third vertex,

when 0.1030≥r>0, coordinates (x,y,z) fall within a figure surrounded by straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrFr, FrE′r, E′rEr, and ErIr, which connect the following 8 points, or fall on any of the straight lines:

point Ir (70.3, 1.0, 28.7),
point I′r (63.8, 5.0, 31.2),
point Jr (57.1, 10.0, 32.9),
point J′r (51.6, 15.0, 33.4),
point Kr (45.4, 21.8, 32.8),
point Fr (−17.476r+2.8, 21.6, 17.476r+75.6),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78),

when 1.0>r>0.103, coordinates (x,y,z) fall within a figure surrounded by straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrBr, BrFr, FrE′r, E′rEr and ErIr, which connect the following 9 points, or fall on any of the straight lines:

point Ir (70.3, 1.0, 28.7),
point I′r (63.8, 5.0, 31.2),
point Jr (57.1, 10.0, 32.9),
point J′r (51.6, 15.0, 33.4),
point Kr (45.4, 21.8, 32.8),
point Br (1.0, 0.1885r2+0.0694+21.543, −0.1885r2−0.0694+77.457)
point Fr (1.0, 1.6787r2−15.118r+23.139, −1.6787r2+15.118r+75.861),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78).

It is also understood that a mixed refrigerant has a refrigerating capacity of 70% or more relative to R404A and is classified under the category of ASHRAE lower flammability when the mixed refrigerant is represented as follows: when the mass % of HFO-1132(E) is x, the mass % of R32 is y, and the total mass % of R1234ze and R1234yf is z based on the sum of HFO-1132(E), R32,

R1234ze, and R1234yf, and r=R1234yf/(R1234ze+R1234yf) in the mixed refrigerant,

in a ternary composition diagram having HFO-1132(E) as a first vertex, R32 as a second vertex, and the sum of 1234ze and R1234yf as a third vertex,

when 0.1030≥r>0, coordinates (x,y,z) fall within a figure surrounded by straight LrI′r, L′rMr, MrM′r, M′rNr, NrFr, FrE′r, E′rEr, and ErIr, which connect the following 8 points, or fall on any of the straight lines:

point Lr (−5.5999r2+20.0r+34.87, 1.0, 5.5999r2−20.0r+64.2),
point L′r (−4.5644r2+18.673r+25.41, 5.0, 4.5644r2−18.673r+69.59),
point Mr (−3.8003r2+15.899r+20.401, 10.0, 3.8003r2−15.899r+69.599),
point M′r (−3.0027r2+13.693r+18.309, 15.0, 3.0027r2−13.693r+66.691),
point Nr (−1.7082r2+11.022r+17.134, 0.3345r+21.594, 1.7082r2−11.3565r+61.272),
point Fr (−17.476r+2.8, 21.6, 17.476r+75.6),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78),

when 1.0>r>0.103, coordinates (x,y,z) fall within a figure surrounded by straight lines LrL′r, L′rMr, MrM′r, M′rNr, NrBr, BrFr, FrE′r, E′rEr, and ErIr, which connect the following 9 points, or fall on any of the straight lines:

point Lr (−5.5999r2+20.0r+34.87, 1.0, 5.5999r2−20.0r+64.2),
point L′r (−4.5644r2+18.673r+25.41, 5.0, 4.5644r2−18.673r+69.59),
point Mr (−3.8003r2+15.899r+20.401, 10.0, 3.8003r2−15.899r+69.599),
point M′r (−3.0027r2+13.693r+18.309, 15.0, 3.0027r2−13.693r+66.691),
point Nr (−1.7082r2+11.022r+17.134, 0.3345r+21.594, 1.7082r2−11.3565r+61.272),
point Br (1.0, 0.1885r2+0.0694r+21.543, −0.1885r2−0.0694r+77.457)
point Fr (1.0, 1.6787r2−15.118r+23.139, −1.6787r2+15.118r+75.861),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78).

Example C

Mixed refrigerants were prepared such that the mass % of HFO-1132(E), the mass % of R32, and the total mass % of R1234ze and R1234yf were as shown in Tables 8 to 11 based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and evaluated in the same manner as in Example A. Tables 8 to 11 show the results. The alphabetical letter “r” represents R1234yf/(R1234ze+R1234yf).

TABLE 8 Com Com Com Com Com Exam- Exam- Exam- Item Unit Ex22 Ex23 Ex24 Ex25 Ex26 ple44 ple45 ple46 HFO-1132 (E) Mass % 70.0 65.0 60.0 55.0 50.0 60.0 55.0 50.0 R32 Mass % 5.0 10.0 15.0 20.0 25.0 5.0 10.0 15.0 R1234ze (r = 0) Mass % 25.0 25.0 25.0 25.0 25.0 35.0 35.0 35.0 GWP — 36 70 103 137 171 36 70 104 COP Ratio % (Relative 106 106 106 106 107 107 107 107 to R404A) Refrigerating % (Relative 126 129 132 135 137 113 116 119 Capacity Ratio to R404A) Condensation ° C. 4.0 4.3 4.5 4.5 4.6 5.8 6.1 6.3 Glide Exam- Com Exam- Exam- Exam- Exam- Com Exam- Item Unit ple47 Ex27 ple48 ple49 ple50 ple51 Ex28 ple52 HFO-1132 (E) Mass % 45.0 40.0 55.0 50.0 45.0 40.0 35.0 50.0 R32 Mass % 20.0 25.0 5.0 10.0 15.0 20.0 25.0 5.0 R1234ze (r = 0) Mass % 35.0 35.0 40.0 40.0 40.0 40.0 40.0 45.0 GWP — 138 171 37 70 104 138 172 37 COP Ratio % (Relative 108 108 107 108 108 108 108 108 to R404A) Refrigerating % (Relative 121 124 107 110 112 115 117 101 Capacity Ratio to R404A) Condensation ° C. 6.4 6.5 6.6 7.0 7.3 7.4 7.4 7.5 Glide Exam- Exam- Exam- Com Exam- Exam- Exam- Exam- Item Unit ple53 ple54 ple55 Ex29 ple56 ple57 ple58 ple59 HFO-1132 (E) Mass % 45.0 40.0 35.0 30.0 45.0 40.0 35.0 30.0 R32 Mass % 10.0 15.0 20.0 25.0 5.0 10.0 15.0 20.0 R1234ze (r = 0) Mass % 45.0 45.0 45.0 45.0 50.0 50.0 50.0 50.0 GWP — 71 104 138 172 37 71 105 138 COP Ratio % (Relative 108 108 109 109 108 109 109 109 to R404A) Refrigerating % (Relative 104 106 108 110 95 97 100 102 Capacity Ratio to R404A) Condensation ° C. 7.9 8.2 8.3 8.3 8.3 8.8 9.1 9.2 Glide Com Exam- Exam- Exam- Exam- Com Exam- Exam- Item Unit Ex30 ple60 ple61 ple62 ple63 Ex31 ple64 ple65 HFO-1132 (E) Mass % 25.0 40.0 35.0 30.0 25.0 20.0 35.0 30.0 R32 Mass % 25.0 5.0 10.0 15.0 20.0 25.0 5.0 10.0 R1234ze (r = 0) Mass % 50.0 55.0 55.0 55.0 55.0 55.0 60.0 60.0 GWP — 172 37 71 105 139 172 38 71 COP Ratio % (Relative 110 109 109 110 110 111 110 110 to R404A) Refrigerating % (Relative 104 89 91 94 96 97 83 85 Capacity Ratio to R404A) Condensation ° C. 9.2 9.1 9.6 9.9 10.0 9.9 9.8 10.3 Glide Exam- Exam- Com Exam- Exam- Exam- Exam- Com Item Unit ple66 ple67 Ex32 ple68 ple69 ple70 ple71 Ex33 HFO-1132 (E) Mass % 25.0 20.0 15.0 30.0 25.0 20.0 15.0 10.0 R32 Mass % 15.0 20.0 25.0 5.0 10.0 15.0 20.0 25.0 R1234ze (r = 0) Mass % 60.0 60.0 60.0 65.0 65.0 65.0 65.0 65.0 GWP — 105 139 173 38 72 105 139 173 COP Ratio % (Relative 110 111 111 110 110 111 111 112 to R404A) Refrigerating % (Relative 87 89 91 77 79 81 83 85 Capacity Ratio to R404A) Condensation ° C. 10.6 10.7 10.6 10.4 10.9 11.2 11.2 11.0 Glide Exam- Exam- Exam- Exam- Com Com Com Com Item Unit ple72 ple73 ple74 ple75 Ex34 Ex35 Ex36 Ex37 HFO-1132 (E) Mass % 25.0 20.0 15.0 10.0 5.0 15.0 10.0 5.0 R32 Mass % 5.0 10.0 15.0 20.0 25.0 5.0 10.0 15.0 R1234ze (r = 0) Mass % 70.0 70.0 70.0 70.0 70.0 80.0 80.0 80.0 GWP — 38 72 106 139 173 39 72 106 COP Ratio % (Relative 110 111 111 112 113 111 112 112 to R404A) Refrigerating % (Relative 71 73 75 77 78 59 61 63 Capacity Ratio to R404A) Condensation ° C. 10.8 11.3 11.5 11.4 11.1 10.6 11.1 112 Glide

TABLE 9 Com Com Com Com Com Exam- Exam- Exam- Item Unit Ex38 Ex39 Ex40 Ex41 Ex42 ple76 ple77 ple78 HFO-1132 (E) Mass % 70.0 65.0 60.0 55.0 50.0 60.0 55.0 50.0 R32 Mass % 5.0 10.0 15.0 20.0 25.0 5.0 10.0 15.0 R1234(ze + yf) Mass % 25.0 25.0 25.0 25.0 25.0 35.0 35.0 35.0 r = 0.103 GWP — 36 70 103 137 171 36 70 104 COP Ratio % (Relative 106 106 106 106 107 107 107 107 to R404A) Refrigerating % (Relative 127 131 133 136 138 115 118 120 Capacity Ratio to R404A) Condensation ° C. 3.8 4.1 4.2 4.3 4.3 5.4 5.8 6.0 Glide Exam- Com Exam- Exam- Exam- Exam- Com Exam- Item Unit ple79 Ex43 ple80 ple81 ple82 ple83 Ex44 ple84 HFO-1132 (E) Mass % 45.0 40.0 55.0 50.0 45.0 40.0 35.0 50.0 R32 Mass % 20.0 25.0 5.0 10.0 15.0 20.0 25.0 5.0 R1234(ze + yf) Mass % 35.0 35.0 40.0 40.0 40.0 40.0 40.0 45.0 r = 0.103 GWP — 137 171 37 70 104 138 171 37 COP Ratio % (Relative 107 108 107 107 108 108 108 108 to R404A) Refrigerating % (Relative 123 125 109 111 114 116 119 102 Capacity Ratio to R404A) Condensation ° C. 6.1 6.1 6.3 6.6 6.9 7.0 7.0 7.1 Glide Exam- Exam- Exam- Com Exam- Exam- Exam- Exam- Item Unit ple85 ple86 ple87 Ex45 ple88 ple89 ple90 ple91 HFO-1132 (E) Mass % 45.0 40.0 35.0 30.0 45.0 40.0 35.0 30.0 R32 Mass % 10.0 15.0 20.0 25.0 5.0 10.0 15.0 20.0 R1234(ze + yf) Mass % 45.0 45.0 45.0 45.0 50.0 50.0 50.0 50.0 r = 0.103 GWP — 71 104 138 172 37 71 104 138 COP Ratio % (Relative 108 108 108 109 108 108 109 109 to R404A) Refrigerating % (Relative 105 108 110 112 96 99 102 104 Capacity Ratio to R404A) Condensation ° C. 7.5 7.8 7.9 7.9 7.9 8.3 8.6 8.7 Glide Com Exam- Exam- Exam- Exam- Com Exam- Exam- Item Unit Ex46 ple92 ple93 ple94 ple95 Ex47 ple96 ple97 HFO-1132 (E) Mass % 25.0 40.0 35.0 30.0 25.0 20.0 35.0 30.0 R32 Mass % 25.0 5.0 10.0 15.0 20.0 25.0 5.0 10.0 R1234(ze + yf) Mass % 50.0 55.0 55.0 55.0 55.0 55.0 60.0 60.0 r = 0.103 GWP — 172 37 71 105 138 172 38 71 COP Ratio % (Relative 109 109 109 109 110 110 109 109 to R404A) Refrigerating % (Relative 106 90 93 95 98 99 85 87 Capacity Ratio to R404A) Condensation ° C. 8.7 8.6 9.1 9.4 9.5 9.4 9.3 9.8 Glide Exam- Exam- Com Exam- Exam- Exam- Exam- Com Item Unit ple98 ple99 Ex48 ple100 ple101 ple102 ple103 Ex49 HFO-1132 (E) Mass % 25.0 20.0 15.0 30.0 25.0 20.0 15.0 10.0 R32 Mass % 15.0 20.0 25.0 5.0 10.0 15.0 20.0 25.0 R1234(ze + yf) Mass % 60.0 60.0 60.0 65.0 65.0 65.0 65.0 65.0 r = 0.103 GWP — 105 139 172 38 72 105 139 173 COP Ratio % (Relative 110 110 111 110 110 110 111 111 to R404A) Refrigerating % (Relative 89 91 93 79 81 83 85 87 Capacity Ratio to R404A) Condensation ° C. 10.1 10.1 10.0 9.9 10.4 10.6 10.7 10.4 Glide Exam- Exam- Exam- Exam- Com Com Com Com Item Unit ple104 ple105 ple106 ple107 Ex50 Ex51 Ex52 Ex53 HFO-1132 (E) Mass % 25.0 20.0 15.0 10.0 5.0 15.0 10.0 5.0 R32 Mass % 5.0 10.0 15.0 20.0 25.0 5.0 10.0 15.0 R1234(ze + yf) Mass % 70.0 70.0 70.0 70.0 70.0 80.0 80.0 80.0 r = 0.103 GWP — 38 72 105 139 173 39 72 106 COP Ratio % (Relative 110 110 111 111 112 111 111 112 to R404A) Refrigerating % (Relative 73 75 77 79 80 61 63 65 Capacity Ratio to R404A) Condensation ° C. 10.3 10.8 11.0 10.9 10.6 10.2 10.7 10.8 Glide

TABLE 11 Com Com Com Com Com Exam- Exam- Exam- Item Unit Ex54 Ex55 Ex56 Ex57 Ex58 ple108 ple109 ple110 HFO-1132 (E) Mass % 70.0 65.0 60.0 55.0 50.0 60.0 55.0 50.0 R32 Mass % 5.0 10.0 15.0 20.0 25.0 5.0 10.0 15.0 R1234(ze + yf) Mass % 25.0 25.0 25.0 25.0 25.0 35.0 35.0 35.0 r = 0.5 GWP — 36 69 103 137 171 36 70 104 COP Ratio % (Relative 106 106 106 106 106 106 106 106 to R404A) Refrigerating % (Relative 132 135 138 141 144 121 124 127 Capacity Ratio to R404A) Condensation ° C. 2.9 3.1 3.2 3.3 3.2 4.2 4.5 4.6 Glide Exam- Com Exam- Exam- Exam- Exam- Com Exam- Item Unit ple111 Ex59 ple112 ple113 ple114 ple115 Ex60 ple116 HFO-1132 (E) Mass % 45.0 40.0 55.0 50.0 45.0 40.0 35.0 50.0 R32 Mass % 20.0 25.0 5.0 10.0 15.0 20.0 25.0 5.0 R1234(ze + yf) Mass % 35.0 35.0 40.0 40.0 40.0 40.0 40.0 45.0 r = 0.5 GWP — 137 171 36 70 104 137 171 37 COP Ratio % (Relative 106 107 106 106 106 107 107 106 to R404A) Refrigerating % (Relative 129 132 115 118 121 123 126 109 Capacity Ratio to R404A) Condensation ° C. 4.6 4.6 4.9 5.2 5.3 5.4 5.3 5.5 Glide Exam- Exam- Exam- Com Exam- Exam- Exam- Exam- Item Unit ple117 ple118 ple119 Ex61 ple120 ple121 ple122 ple123 HFO-1132 (E) Mass % 45.0 40.0 35.0 30.0 45.0 40.0 35.0 30.0 R32 Mass % 10.0 15.0 20.0 25.0 5.0 10.0 15.0 20.0 R1234(ze + yf) Mass % 45.0 45.0 45.0 45.0 50.0 50.0 50.0 50.0 r = 0.5 GWP — 70 104 138 171 37 70 104 138 COP Ratio % (Relative 107 107 107 107 107 107 107 108 to R404A) Refrigerating % (Relative 112 115 117 120 104 106 109 111 Capacity Ratio to R404A) Condensation ° C. 5.9 6.0 6.1 6.0 6.2 6.6 6.8 6.8 Glide Com Exam- Exam- Exam- Exam- Com Exam- Exam- Exam- Item Unit Ex50 ple124 ple125 ple126 ple127 Ex62 ple128 ple129 ple130 HFO-1132 (E) Mass % 25.0 40.0 35.0 30.0 25.0 20.0 35.0 30.0 25.0 R32 Mass % 25.0 5.0 10.0 15.0 20.0 25.0 5.0 10.0 15.0 R1234(ze + yf) Mass % 50.0 55.0 55.0 55.0 55.0 55.0 60.0 60.0 60.0 r = 0.5 GWP — 172 37 71 104 138 172 37 71 105 COP Ratio % (Relative 108 107 107 108 108 108 107 108 108 to R404A) Refrigerating % (Relative 114 98 101 103 105 107 92 95 97 Capacity Ratio to R404A) Condensation ° C. 6.7 6.9 7.3 7.4 7.5 7.3 7.5 7.9 8.1 Glide Exam- Com Exam- Exam- Exam- Exam- Com Exam- Exam- Item Unit ple131 Ex63 ple132 ple133 ple134 ple135 Ex64 ple136 ple137 HFO-1132 (E) Mass % 20.0 15.0 30.0 25.0 20.0 15.0 10.0 25.0 20.0 R32 Mass % 20.0 25.0 5.0 10.0 15.0 20.0 25.0 5.0 10.0 R1234(ze + yf) Mass % 60.0 60.0 65.0 65.0 65.0 65.0 65.0 70.0 70.0 r = 0.5 GWP — 138 172 37 71 105 138 172 38 71 COP Ratio % (Relative 109 109 108 108 109 109 110 108 108 to R404A) Refrigerating % (Relative 99 101 86 89 91 93 95 80 83 Capacity Ratio to R404A) Condensation ° C. 8.1 7.9 8.0 8.5 8.6 8.6 8.3 8.4 8.9 Glide Exam- Exam- Com Exam- Exam- Exam- Exam- Com Com Item Unit ple138 ple139 Ex65 ple140 ple141 ple142 ple143 Ex66 Ex67 HFO-1132 (E) Mass % 15.0 10.0 5.0 20.0 15.0 10.0 5.0 10.0 5.0 R32 Mass % 15.0 20.0 25.0 5.0 10.0 15.0 20.0 5.0 10.0 R1234(ze + yf) Mass % 70.0 70.0 70.0 75.0 75.0 75.0 75.0 85.0 85.0 r = 0.5 GWP — 105 139 172 38 71 105 139 38 72 COP Ratio % (Relative 109 109 110 108 109 109 110 109 109 to R404A) Refrigerating % (Relative 85 87 89 75 77 79 81 63 65 Capacity Ratio to R404A) Condensation ° C. 9.0 8.9 8.6 8.6 9.1 9.3 9.1 8.2 8.7 Glide

DESCRIPTION OF THE REFERENCE NUMERALS

  • 1: Sample cell
  • 2: High-speed camera
  • 3: Xenon lamp
  • 4: Collimating lens
  • 5: Collimating lens
  • 6: Ring filter

Claims

1. A composition comprising a refrigerant, the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), and 1,3,3,3-tetrafluoropropene (R1234ze).

2. The composition according to claim 1, wherein point I (70.3, 1.0, 28.7), point J (57.1, 10.0, 32.9), point K (45.4, 21.8, 32.8), point F (2.8, 21.6, 75.6), and point E (30.2, 1.0, 68.8),

when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments IJ, JK, KF, FE, and EI, which connect the following 5 points, or fall on any of the line segments:
line segments KF and EI are straight lines,
coordinates (x,y,z) of a point on line segment IJ are represented by (x, 0.00991x2−1.945x+88.734, −0.00991x2+0.945x+11.266),
coordinates (x,y,z) of a point on line segment JK are represented by (x, 0.01605x2−2.6528x+109.17, −0.01605x2+1.6528x-9.17), and
coordinates (x,y,z) of a point on line segment FE are represented by (x, 0.0017x2−0.8094x+23.852, −0.0017x2−0.1906x+76.148).

3. The composition according to claim 1, wherein point I (70.3, 1.0, 28.7), point J (57.1, 10.0, 32.9), point K (45.4, 21.8, 32.8), point D (10.7, 21.6, 67.7), and point C (38.6, 1.0, 60.4),

when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments IJ, JK, KD, DC, and CI, which connect the following 5 points, or fall on any of the line segments:
line segments KD and CI are straight lines,
coordinates (x,y,z) of a point on line segment IJ are represented by (x, 0.00991x2−1.945x+88.734, −0.00991x2+0.945x+11.266),
coordinates (x,y,z) of a point on line segment JK are represented by (x, 0.01605x2−2.6528x+109.17, −0.01605x2+1.6528x−9.17), and
coordinates (x,y,z) of a point on line segment DC are represented by (x, 0.00195x2−0.8346x+30.307, −0.00195x2−0.1654x+69.693).

4. The composition according to claim 1, wherein point L (34.8, 1.0, 64.2), point M (20.4, 10.0, 69.6), point N (17.1, 21.6, 61.3), point F (2.8, 21.6, 75.6), and point E (30.2, 1.0, 68.8),

when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments LM, MN, NF, FE, and EL, which connect the following 5 points, or fall on any of the line segments:
line segments NF and EL are straight lines,
coordinates (x,y,z) of a point on line segment LM are represented by (x, 0.0399x2−2.8271x+51.071, −0.0399x2+1.8271x+48.929),
coordinates (x,y,z) of a point on line segment MN are represented by (x, 0.9452x2−38.959x+411.42, −0.9452x2+37.959x-311.42), and
coordinates (x,y,z) of a point on line segment FE are represented by (x, 0.0017x2−0.8094x+23.852, −0.0017x2−0.1906x+76.148).

5. The composition according to claim 1, wherein point O (18.1, 15.8, 66.1), point N (17.1, 21.6, 61.3), and point D (10.7, 21.6, 67.7),

when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments ON, ND, and DO, which connect the following 3 points, or fall on any of line segments ON, ND, and DO:
line segment ND is a straight line,
coordinates (x,y,z) of a point on line segment ON are represented by (x, 0.9452x2−38.959x+411.42, −0.9452x2+37.959x-311.42), and
coordinates (x,y,z) of a point on line segment DO are represented by (x, 0.00195x2−0.8346x+30.307, −0.00195x2−0.1654x+69.693).

6. The composition according to claim 1, wherein the refrigerant further comprises 2,3,3,3-tetrafluoropropene (R1234yf).

7. The composition according to claim 6, wherein point Ir (70.3, 1.0, 28.7), point I′r (63.8, 5.0, 31.2), point Jr (57.1, 10.0, 32.9), point Fr (51.6, 15.0, 33.4), point Kr (45.4, 21.8, 32.8), point Fr (−17.476r+2.8, 21.6, 17.476r+75.6), point Er (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78), point Ir (70.3, 1.0, 28.7), point I′r (63.8, 5.0, 31.2), point Jr (57.1, 10.0, 32.9), point Fr (51.6, 15.0, 33.4), point Kr (45.4, 21.8, 32.8), point Br (1.0, 0.1885r2+0.0694+21.543, −0.1885r2−0.0694+77.457) point Fr (1.0, 1.6787r2−15.118r+23.139, −1.6787r2+15.118r+75.861), point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78).

when the mass % of HFO-1132(E) is x, the mass % of R32 is y, and the total mass % of R1234ze and R1234yf is z based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and r=R1234yf/(R1234ze+R1234yf) in the refrigerant,
in a ternary composition diagram having HFO-1132(E) as a first vertex, R32 as a second vertex, and the sum of 1234ze and R1234yf as a third vertex,
when 0.103≥r>0, coordinates (x,y,z) fall within a figure surrounded by straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrFr, FrE′r, E′rEr, and ErIr, which connect the following 8 points, or fall on any of the straight lines:
when 1.0>r>0.103, coordinates (x,y,z) fall within a figure surrounded by straight lines IrI′r, I′rJr, JrJ′r, J′rKr, BrFr, FrE′r, E′rEr, and ErIr, which connect the following 9 points, or fall on any of the straight lines:

8. The composition according to claim 6, wherein point Lr (−5.5999r2+20.0r+34.87, 1.0, 5.5999r2−20.0r+64.2), point L′r (−4.5644r2+18.673r+25.41, 5.0, 4.5644r2−18.673r+69.59), point Mr (−3.8003r2+15.899r+20.401, 10.0, 3.8003r2−15.899r+69.599), point M′r (−3.0027r2+13.693r+18.309, 15.0, 3.0027r2−13.693r+66.691), point Nr (−1.7082r2+11.022r+17.134, 0.3345r+21.594, 1.7082r2−11.3565r+61.272), point Fr (−17.476r+2.8, 21.6, 17.476r+75.6), point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78), point Lr (−5.5999r2+20.0r+34.87, 1.0, 5.5999r2−20.0r+64.2), point L′r (−4.5644r2+18.673r+25.41, 5.0, 4.5644r2−18.673r+69.59), point Mr (−3.8003r2+15.899r+20.401, 10.0, 3.8003r2−15.899r+69.599), point M′r (−3.0027r2+13.693r+18.309, 15.0, 3.0027r2−13.693r+66.691), point Nr (−1.7082r2+11.022r+17.134, 0.3345r+21.594, 1.7082r2−11.3565r+61.272), point Br (1.0, 0.1885r2+0.0694r+21.543, −0.1885r2−0.0694r+77.457) point Fr (1.0, 1.6787r2−15.118r+23.139, −1.6787r2+15.118r+75.861), point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78).

when the mass % of HFO-1132(E) is x, the mass % of R32 is y, and the total mass % of R1234ze and R1234yf is z based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and r=R1234yf/(R1234ze+R1234yf) in the refrigerant,
in a ternary composition diagram having HFO-1132(E) as a first vertex, R32 as a second vertex, and the sum of 1234ze and R1234yf as a third vertex,
when 0.103≥r>0, coordinates (x,y,z) fall within a figure surrounded by straight lines LrI′r, L′rM′r, MrM′r, M′rNr, NrFr, FrE′r, E′rEr, and ErIr, which connect the following 8 points, or fall on any of the straight lines:
when 1.0>r>0.103, coordinates (x,y,z) fall within a figure surrounded by straight lines LrL′r, L′rMr, MrM′r, M′rNr, NrBr, BrFr, FrE′r, E′rEr, and ErIr, which connect the following 9 points, or fall on any of the straight lines:

9. The composition according to claim 1, which is for use as a working fluid for a refrigerating machine, the composition further comprising a refrigeration oil.

10. The composition according to claim 1, which is for use as an alternative refrigerant for R404A.

11. Use of the composition of claim 1 as an alternative refrigerant for R404A.

12. A refrigerating machine comprising the composition of claim 1 as a working fluid.

13. A method for operating a refrigerating machine, comprising circulating the composition of claim 1 as a working fluid in a refrigerating machine.

Patent History
Publication number: 20220145154
Type: Application
Filed: Dec 15, 2021
Publication Date: May 12, 2022
Applicant: DAIKIN INDUSTRIES, LTD. (Osaka)
Inventors: Mitsushi ITANO (Osaka), Shun OHKUBO (Osaka), Daisuke KARUBE (Osaka)
Application Number: 17/551,822
Classifications
International Classification: C09K 5/04 (20060101);